CH660365A5 - TRICYCLOHEXYLETAIN BENZOATE AS ORGANIC TIN DERIVATIVE. - Google Patents

Description

The present invention relates to a new organic derivative of tin as well as its method of preparation, the compositions insertici- ~ des and acaricides containing it and a method of treating plants with these compositions for their protection against insects and phytophagous mites.

Tricyclohexyltin hydroxide, better known by its common name cyhexatin, is a miticide known remarkable for its specific effectiveness against phytophagous mites in particular in arboriculture, in vegetable or ornamental culture. This product is used in the form of a wettable powder and more recently as an emulsifiable concentrate. However, the latter formula is difficult to obtain due to the insolubility of cyhexatin in most of the usual solvents in agrochemicals. We are therefore led to use complicated emulsifying systems which do not provide the formula with truly satisfactory stability.

We have now discovered a new active ingredient consisting of an organic derivative of tin which also has excellent acaricide activity and which moreover lends itself, and surprisingly, very easily to a formulation in the form of an emulsifiable concentrate due to its remarkable solubility in the usual solvents in agrochemistry.

The subject of the invention is therefore a new organic derivative of tin consisting of tricyclohexyltin benzoate. It also relates to acaricide compositions containing this product as active material, and in particular emulsifiable concentrates, which can be used for the treatment of plants against phytophagous mites.

Tricyclohexyltin benzoate is a compound of formula:

(o); s ° -0 - rO

It can be prepared by the action of benzoic acid on tricyclohexyltin hydroxide. This reaction is carried out in an organic solvent medium such as toluene, xylene, chlorobenzene, polychlo-robenzene or even cyclohexanone, at a temperature generally at most equal to 60 ° C. The water formed during the reaction is eliminated, as and as it forms, for example by absorption with a water-soluble salt such as sodium or magnesium sulfate or by azeotropic distillation of the solvent-water mixture. The product obtained and isolated is in the form of a white crystallized powder with a melting point of 111 ° C.

The following examples illustrate, on the one hand, the preparation and the physicochemical properties of the compound according to the invention, in particular

The announced structure is confirmed by infrared spectrometric analysis and proton NMR.

25 Example 2:

An emulsifiable concentrate having the following composition is prepared, for one liter of formula:

- Tricyclohexyltin benzoate

- Calcium dodecyl benzene sulfonate in 60% solution in isopropanol

- Castor oil ethoxylated with 30-33 moles of ethylene oxide

- Xylene

Density at 20 ° C: 1.008.

411 g

50g

50 g 498 g

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Example 3:

546 g of cyclohexanone and 316 g of 94% tricyclohexyltin hydroxide are charged at 50 ° C. with stirring. We do not obtain the dissolution of the tin derivative. 95 g of benzoic acid are then added while maintaining the temperature at 50 ° C. After 10 minutes of stirring, a yellow solution is obtained which, after filtration and drying, leads to a clear solution. By adding emulsifiers as in the previous example, an emulsifiable concentrate with a density at 20 ° C.: 1.057 is obtained.

Example 4:

By operating as in the previous example, the same observations are made, starting from the following mixture:

n / a - Tricyclohexyltin benzoate

- Acetophenone

- Xylene

- Calcium dodecyl benzene sulfonate in 60% solution in isopropanol

55 - Castor oil ethoxylated (30-33 moles)

4111 285 s 279 d

50! 50 I

An emulsifiable concentrate is obtained with a density at 20 ° C equal to 1.075.

60 Example 5: Miticide tests

Bean seedlings in the 1 leaf trifoliate stage are contaminated with a mixed population of Tetranychns urticae.

After 48 hours, the contaminated plants are treated with a FISCHER type spray gun, up to the limit of runoff, with aqueous dilutions of the compositions to be tested. These consist of:

a) by way of reference, a commercial composition PLIC-TRAN 600 F, aqueous suspension concentrated to 600 g / 1 of cyhexatin,

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660 365

b) the emulsifiable concentrate according to the invention obtained in Example 3.

Three bean plants are used per product and per dose. The treated plants are kept for 14 days in a greenhouse (temperature 20-25 "C, relative humidity 40-60%, illumination 5 to 10,000 lux). Water is applied at the foot of these plants to avoid any leaching of the products.

For each plant, the mite population present is estimated in relation to the average of the 3 controls, treated with water only, after 2, 7 and 14 days after treatment. We deduce a percentage of efficiency.

c i mno / Population of the treated plant

Example: 100% —-i- r in%

Untreated plant population

Under these conditions, the results recorded in the following table are observed:

Product

Active ingredient

% efficiency at n days in g / hl

2

7

14

30

90

100

100

Reference

15

70

90

100

5

50

90

90

30

80

100

100

Invention

15

80

100

100

5

50

80

80

Witness

0

0

0

0

In addition, no phytotoxicity was noted.

By operating in the same way on another species of mites, Polyphagotarsonemus, we see that the lethal dose at 90%, in ppm, is 10 for tricyclohexyltin benzoate is eight times less than for the reference cyhexatin (used in powder wet).

Example 6: Insecticide test

Turnip leaf discs are placed in agar in petri dishes. In each one places 10 larvae of Pluteïla xy-listella on each disc, which is covered by a ventilated cover. The product to be tested is dissolved in a 50/50 water-acetone mixture and the disks are treated by spraying with this solution using Potter's tower at a dose equivalent to 675 liters / ha. The discs are kept at 26 ° C. 4-8 hours after treatment, the live and dead larvae are counted and the percentage of mortality is calculated.

Under these conditions, it is observed that at a dose of 100 g / hl tricyclohexyltin benzoate causes a mortality of at least 95% while, at the same dose, the cyhexatin taken as reference in the form of a wettable powder is practically inactive (<10%).

These examples clearly show:

The remarkable solubility of the compound according to the invention, making it easy to introduce it into formulations of the emulsifiable concentrate type, allowing association with other agrochemical active materials,

- the excellent acaricidal efficacy of the compound according to the invention, more versatile than the reference,

- a complementary insecticide activity that the reference does not have.

This' compound is therefore usable for the fight against insects and more particularly phytophagous mites in crops such as in particular vine, arboriculture, vegetable and ornamental crops.

They advantageously apply at doses of 0.05 to 5 kg / ha, preferably from 0.1 to 2 kg / ha.

For its practical use, the compound according to the invention is rarely used alone. Most often, it is part of compositions. These compositions, which can be used for the protection of plants against fungal diseases, contain as active material the compound according to the invention as described above in combination with solid or liquid carriers, acceptable in agriculture and surfactants also acceptable in agriculture . In particular, the usual inert supports and the usual surfactants can be used.

These compositions can also contain all kinds of other ingredients such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, stabilizers, sequestrants, etc., as well as others. known active ingredients with pesticidal properties (especially insecticides or fungicides) or with properties promoting plant growth (especially fertilizers) or with properties that regulate plant growth. More generally, the compounds according to the invention can be combined with all the solid or liquid additives corresponding to the usual techniques of formulation.

In general, compositions containing 0.5 to 5000 ppm of active substance are very suitable; these values are indicated for the compositions ready for application (“ppm” means “part per million”). The area from 0.5 to 5000 ppm corresponds to an area of 5 × 10 −5% to 0.5% ( weight percentages).

As regards the compositions suitable for storage and transport, they more advantageously contain from 0.5 to 95% (by weight) of active substance.

Thus, the compositions for agricultural use according to the invention can contain the active materials according to the invention within very wide limits, ranging from 5 • 10 ~ 5% to 95% (by weight).

According to what has already been said, the compounds according to the invention are generally combined with supports and optionally surfactants.

By the term “support”, in the present description, is meant an organic or mineral, natural or synthetic material, with which the active material is associated to facilitate its application to the plant, to seeds or to the soil. This support is therefore generally inert and it must be acceptable in agriculture, in particular on the treated plant. The support can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, etc. .).

The surfactant can be an emulsifying, dispersing or wetting agent of ionic or nonionic type. Mention may be made, for example, of polyacrylic acid salts, salts of lignosulfonic acids, salts of phenylsulfonic or naphthalene sulfonic acids, polycondensates of ethylene oxide on fatty alcohols or on fatty acids or on fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulfosuccinic acid esters, taurine derivatives (especially alkyltaurates), phosphoric esters of alcohols or of po-lyoxyethylated phenols . The presence of at least one surfactant is generally essential when the active material and / or the inert support are not soluble in water and the vector agent for the application is water.

For its application, the compound of the invention is therefore generally in the form of compositions; these compositions according to the invention are themselves in fairly diverse forms, solid or liquid.

As forms of solid compositions, mention may be made of powders for dusting or dispersion (with a content of compound of formula (I) which can range up to 100%) and granules, in particular those obtained by extrusion, by compacting, by impregnation of a granulated support, by granulation from a powder (the content of compound of formula (I) in these granules being between 1 and 80% for the latter cases).

As forms of liquid compositions or intended to constitute liquid compositions during application, mention may be made of solutions, in particular emulsifiable concentrates, formulas

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660 365

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at very low volume (or ULV), emulsions, concentrated suspensions, aerosols, wettable powders (or spray powder), pastes.

The emulsifiable concentrates most often comprise 10 to 80% of active material, the emulsions or solutions ready for application containing, for their part, 0.01 to 20% of active material. In addition to the solvent, emulsifiable concentrates can contain, when necessary, 2 to 20% of suitable additives, such as stabilizers, surfactants, penetrating agents, corrosion inhibitors, dyes, adhesives. As an example, here is the composition of some concentrates:

Active ingredient

400 g / 1

Alkaline dodecylbenzene sulfonate

24 g / 1

10-molecule oxyethylated nonylphenol

ethylene oxide

16 g / 1

Cyclohexanone

200 g / 1

Aromatic solvent q.s.p.

1 litre

According to another formula of emulsifiable concentrate, the following are used:

Active ingredient

250 g

Epoxidized vegetable oil

25g

Mixture of alkylaryl sulfonate and

polyglycol ether and fatty alcohols

100g

Dimethylformamide

50g

Xylene

575 g

According to another formula of emulsifiable concentrate, the following are used:

Active ingredient

450 g

Oxyethylated tristyrylphenol

50g

Alkaline dodecylbenzenesulfonate

50g

- Chlorobenzene q.s.p. 1 litre

From these concentrates, emulsions with any desired concentration can be obtained by dilution with water, which are particularly suitable for application to the leaves.

For a so-called “very low volume” (U.L.V.) application with a spray in very fine droplets, solutions are prepared in organic solvents containing from 70 to 99% of active material.

For example, a very low volume formulation having the following composition is prepared:

- Active ingredient 200 g

- Paraffinic / aromatic oil 200 g

- Aromatic solvent q.s.p. 1 litre

Here is another formulation at very low volume:

Tricyclohexyltin benzoate

150g

Cypermethrin

30g

Triazophos

125g

Paraffinic / aromatic oil

150g

Betapinene

19g

Acetic anhydride

15g

Cyclohexanone q.s.p.

1 litre

Concentrated suspensions, also applicable as a spray

tion, are prepared so as to obtain a stable fluid product which does not deposit and they usually contain from 10 to 75% of active material, from 0.5 to 15% of surfactants, from 0.1 to 10% thixotropic agents, from 0 to 10% of suitable additives, such as defoamers, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as support, water or an organic liquid in which the active ingredient is sparingly or not soluble: some organic solids or mineral salts can be dissolved in the support to help prevent sedimentation or as antifreeze for water.

Wettable powders (or spray powder) are usually prepared so that they contain 20 to 95% active ingredient, and they usually contain, in addition to the solid support, 0 to 5% of a wetting agent, 3 10% of a dispersing agent,

and, when necessary, from 0 to 10% of one or more stabilizers and / or other additives, such as penetrating agents, adhesives, or anti-caking agents, colorants, etc.

As an example, here are various compositions of wettable powders:

- Active ingredient 50%

- Calcium lignosulfonate (deflocculant) 5%

- Isopropylnaphthalene sulfonate (anionic wetting agent) 1%

- Anti-clumping silica 5%

- Kaolin (charge) 39%

70% wettable powder:

- Active ingredient 700 g

- Sodium dibutylnaphthylsulfonate 50 g

- Condensation product in 3/2/1 proportions of naphthalene sulfonic acid, phenylsulfonic acid and formaldehyde 30 g

- Kaolin 100 g

- Champagne chalk 120 g

40% wettable powder:

- Active ingredient 400 g

- Sodium lignosulfonate 50 g

- Sodium dibutylnaphthalene sulfonate 10 g

- Silica 540 g

25% wettable powder:

- Active ingredient 250 g

- Calcium lignosulfonate 45 g

- Equal weight mixture of Champagne chalk and hydroxyethylcellulose 19 g

- Sodium dibutylnaphthalene sulfonate 15 g

- Silica 195 g

- Champagne chalk 195 g

- Kaolin 281 g

25% wettable powder:

- Active ingredient 250 g

- Isooctylphenoxy-polyoxyethylene-ethanol 25 g

- Equal weight mixture of Champagne chalk and hydroxyethylcellulose 17 g

- Sodium aluminosilicate 543 g

- Kieselguhr 165 g

10% wettable powder:

- Active ingredient 100 g

- Mixture of sodium salts of saturated fatty acid sulfates 30 g

- Condensation product of naphthalene sulfonic acid and formaldehyde 50 g

- Kaolin 820 g

In order to obtain these wettable powders, the active materials are intimately mixed in appropriate mixers with the additional substances and ground with mills or other suitable mills. This gives powders whose wettability and suspension are advantageous; they can be suspended in water at any desired concentration and this suspension can be used very advantageously in particular for application to the leaves of plants.

As has already been said, aqueous dispersions and emulsions, for example compositions obtained by diluting with water a wettable powder or an emulsifiable concentrate according to the invention, are included in the general scope of the present invention. The emulsions can be of the water-in-oil or oil-in-water type and they can have a thick consistency like that of a "mayonnaise".

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The granules intended to be placed on the ground are usually prepared so that they have dimensions of between 0.1 and 2 mm and they can be produced by agglomeration or impregnation. In general, the granules contain 0.5 to 25% of active material and 0 to 10% of additives such as stabilizers, slow release modifiers, binders and solvents.

The compounds of formula (1) can also be used in the form of powders for dusting; one can also use a composition comprising 50 g of active material and 950 g of talc; one can also use a composition comprising 20 g of active material.

5 10 g of finely divided silica and 970 g of talc; these constituents are mixed and ground and the mixture is applied by dusting.

Claims (6)

660 365 1. Organic derivative of tin, characterized in that it consists of tricyclohexyltin benzoate. 2. Process for the preparation of the compound according to claim 1, characterized in that tricyclohexyltin hydroxide is reacted with benzoic acid, in an organic solvent medium with elimination of the water formed. 2 3. Insecticidal and / or acaricidal composition, characterized in that it contains, as active material, at least the compound according to claim 1. 4. Composition according to claim 3, characterized in that it also contains an insecticidal active material. 5. Composition according to claim 3, characterized in that it is in the form of an emulsifiable concentrate. is 6. A method of treating plants against phytophagous insects and mites, characterized in that a compound according to claim 1 is applied to them. its excellent solubility in most organic solvents, on the other hand its excellent acaricide properties. Example 1: 2326 g (6.04 moles) of tricyclohexyltin hydroxide, 9 liters of anhydrous toluene and 737 g (6.04 moles) of benzoic acid are charged to a 20 liter reactor. The mixture is heated with stirring to 50-60 C for 1 h 30 min, then cooled to room temperature. 1500 g of anhydrous sodium sulfate are then added and the stirring is continued for one hour. Filtered and concentrated under reduced pressure (6 mm Hg = 789 Pa) at 50 ° C. A white solid product precipitates which is recrystallized from 3250 ml of hexane at 50D C. By cooling to 10-15 ° C, the product precipitates. It is wrung and rinsed with 750 ml of cold hexane. After drying in an oven at 30 ° C under reduced pressure (6 mmHg = 789 Pa), 2185 g of tricyclohexyltin benzoate are thus obtained. The hexane filtrate is concentrated and a second stream of 362 g of the product is obtained. Total weight obtained: Yield: Fusion point: 2547 g 86.8% 111 ° C